Manufacture of condensation products of the anthraquinone series



Patented Jan; 13, 1925.

j UNITED .ISVTATESJ PATENT- OFF CE-j EWALD STEINBUCH, OF BASEL, AND FRANZ ACKERMA NN, OF BINNINGEN, NEAR BASEL, SWITZERLAND, ASSIGNORS TO SDQIETY OF CHEMICAL INDUSTRY IN BASLE,

OF BASED, SWITZERLAND.

-MANUFACTURE OF .CONDENS ATION PRODUCTS OF THE ANTHRAQUINONE SERIES.

No Drawing,

scribed a process consisting in treating amino compounds of the anthraquinone series, the amino group of which may also he mono-substituted, with derivatives of 1.3.5-triazine' halogenated in the nucleus, as for instance cyanuric chloride. There are thus obtained valuable condensation products containing 1.3.5-triazine nuclei which may be used partly as colouring matters,

- partly as starting materials for the production of dyestuifs. As a result of further study and experiment on the-lines of the above cited fundamental process we have found that particularly valuable products are obtained by causing amino compounds carrying at least one reactive hydrogen atom in the amino group, to reset on compounds having the general formula:

wherein the letter a represents the radical N halogen- \3-halogen g, I l lll and one of the two letters b a hydrogen atom and the other the radical N halogen- \fi-hulogen I hppuuauon. filed June 10, 1924. Serial No. 719,202.

buch compounds are for instance the condensation product described in Example 15 of the said specification as obtainable froin I one molecular proportion of, 1:5-diaminoanthraquinoueand two molecular proportlons of cyanuric chloride, as well as the corresponding condensation product from l: 8-' d1aminoantlu'aquinone, or from a) technical n'nxture of both, such as is obtained by dinrtrating anthraquinone and reducing the mixture of dinitro-anthraquinones produced. There are thus obtained condensation produ ts of the general formula:

wherein the .leter a represents a radical it t (in which y and z are substituents of which at least one is an amino radical which may he substituted), and wherein one of the two letters b indicates a hydrogen atom and other a radical; i

(in which y and 2 liesubstituents of which at least one IS an amino radical whieh may be substituted), which condensation'products' form brownish-yellow to dark green fpow-lj ders which dissolve in cold concentrated",

sulphuric acid to yellow to hluish'red-browngf iot nitrobenzene to yellow,

solutions, and in to violet, brown and dirty green solutions.

\Vith hydrosulphite and caustic soda, solution they yield red-brown to bordeaux and red-violet vats from which cotton is dyed very fast reddish-yellowto red, brown and,

olive tints.

These dyestuffs are also produced by cansing two molecular proportions of the or different derivatives of 1.3.5-triazine, substituted in the nucleus by halogen, which Halogen may have been in part exchanged I fonafsuitable residue, to react with one of .vention, the parts being by weight 3".- I

the diaminoanthraquinones'f in question The follovvingfexamplesf illustrate the; m-z

. Ewmple- L.

'24 parts of 1 5 diaminoanthraquinone and 250 parts of nitrobenzene are heated together at about 110C. and after addition of a solution, at'l60 80'C.,--of LO-parts of 1 c'yannric chloride 111150 parts of nitroben r .15 1410 145 0., for about an ;hour. The-mixzene the whole isjheated, while stirring, at

ture is then{ cooledand the product which has separated is filtered. It is suspended in 800 partsof nitrobenzene and after addition of 65 parts of l-aminoanthraqu none the mixture is stirred for'48 hours at 140-.

145 C. When cold the product which has been separated isfiltered, washed ,with uitrobenzcne and then Wlth' fll00h0l, andfinally dried. It is a brownish-yellow powder, insoluble in water. and alcohol and.

' sparingly soluble in hot nitrobenzene to a strong reddish-yellow tints. p, 4 If 1: S-diaminoanthraquinone- 15 used m-.

yellow solution. Its solution in -coldconcentrated sulphuric acid is yellow. .It yields a red-brown yat which dyes cotton washed with nitroben'zene and alcohol and dried. It forms a brownish-yellow powder, soluble in concentrated sulphuric. acid to a. yellow solution and givin a red-brown vat which dyes cotton full dish-yellow tints.

Ewample' 3.

24 parts of diaminoanthraquinone ob- -tained by diuitrating anthraquinone and ireduding the mixture of dinitroanthra'quinones produced, are introduced into 250 (3,, and thewhole is heated while stirring for about an hour at 140-145 C. It isarts of. nitroben'zene-and. the mixture is eated .to about 110 C., and then receives anaddition- 01540 parts of-cyanuric chloride dissolved in 15 0 parts-0f nitroben'zene,

the solution'being at a temperature of 60 thencooled and'ithe product which has separated filtered. This product is suspended in about 800 parts of nitrobenzene and after additionof 34 parts of l-amino-Q-zl-anthta- .quinone-acridone and 22.3 parts of 1-aininoi anthraquinone, the mixture isheate'd to the boiling point of .the 'nitrob'enzene for six hours 'while stirring,-'- Aft er cooling, the

solid matter is filtered, then washed with nitrobenzene andfaloohol and'dried. It is a dark green powder-insoluble in water and alcohol, sparingly soluble in' hotnitrobenzene to a dirtygreen'SOlution. Itssolution in cold concentrated sulphuric acid is reddish-brown. Ityield's: a brown-red vat which dyes cotton yellowish-olive tints.

The use ofj-pure 155- or 1:-8-diamino- ,anthraquinone leads to-a very similar con- 'densation" product I -fiwemptel; p 10 parts of-thedyestufi' made as'des'cribed n Example 3 are introduced into. '100 parts of nitrobenzene satura'tedin "the cold with ammoniaand the mixture isheatedfor 24 hours in a closed vessel at 150160 C. After, cooling, the-mass is mixed with some alrohol and filtered and the residue on the filter is washed with: alcohol and dried.

This product is, a greenish blackpowder;

sparingly soluble in most organic solvents;

In concentrated" sulphuric acid it dissolves to a red-brown solution. It forms a -brown--- ish-red vat; which dyes ,cotton brownisholive tints.

' Example 5.

15 .parts of the dyestufi obtained-as described in. Example -3 are introduced into a mixture of 500 parts of aniline and 500 parts of nitrobenzene, and .the whole is e cooling, the con ensation product is filtered,

atedfor a lon time at -150 (1.. After iwashed with nitrobenzene and with alcohol and dried. It-is-a greenish-black ields a. brownish-red, vat dyeing cotton ful brownish-olive tints.

Ewample, 6'.' arts 3 of diaminoanthraquinone obtam by dmitrating anthraquinone and reducing the nitration product produced are introduced, together. with 40 parts of cya nuric chloride, into about 400 parts of nitrobenzene and the wholeis heated forflan hour at PLO- C. After cooling the separated product is filtered. It is now stirred into about 800 parts of nit-robenzene and after addition of 68 parts of 4-amino-2z1- anthraquinoneacridone', the. mixture is heated-for eight hours to the. boiling point:

quinone are then added and the heating to owder-. .WhlOll dissolves in concentrated su phuric -11o; (acid to a red-brown solution and of nitrobenzene. 22 parts of l-aminoanthra-s ;boiling continued for hours. After 1 cooling the condensation product thus obtained is filtered, washed and dried. It 1s a green-black power, insoluble 111 water and alcohol and s mringly soluble in hot nit-roolive shades.

. chloride into about 00 parts of mtrohenzene and the whole is heated for an hour at -14.? C. After cooling the separated product is filtered. It is stirred into about. 800 parts of nitrobenzcne and afteraddition of 34: partsof 4-a1nino-2:1-anthraq'uinone-acridone and 36 parts of 4-amino- 2:1 anthraquinonethioxanthone the whole is" heated for-6 hours to the boiling point of the nitrobenzene. After cooling the congleusation product. thus obtained is filtered, washed'and dried. It is a blackish powder, insoluble,- in water and alcohol, sparin%ly' soluble in hot nitrobenzeneto a violet so tion and soluble in cold concentrated sul-. phuric acid to-a brown-red solution." Its bordeaux-coloured vat dves cotton dark' Example 8. i 24 parts of diaminoanthraquinone; ob-

tained by dinitrating anthraquinone and re-- ducing the nitration product, are introduced to gcthcr with -10 parts of cyanuric chloride into about 400 parts of'nitrobenzene, and the mixture is heated for an hour at 14:0- C. Xfter cooling, the separated prod not is filtered. It is stirred into about 900 parts of nitrobenzene, and after addition of- 72 parts of 4-amino-2zl-anthraquinonethioxanthone the whole is heated for 8 hours to the boiling point of the nitrobenzene. After cooling the finished condensation product is filtered, washed and dried. It is a dark violet powder, insoluble in water and-alcohol, sparingly soluble in hot nitrobenzene to a violet solution and soluble in cold concentrated sulphuric acid to a brownish hluered solution. Its vat is red-violet and dyes cottonbrownish-red tints.

Example 9.

21 parts of diaminoanthraquinone made by dinitrating anthraquinone and reducing the nitration product, are introduced toe; gether with 40 parts of-cyanuric chloride into about 400' parts of nitrobenzene and the mixture is heated for an hour at 140-- 145" 0. After cooling, the separated'prodnot is filtered. It is introduced into 800 parts of nitrobenzene and after addition of 35 parts of Lamina-2:lfanthraquiuoncthioxanthone and 22 parts"of.1 aminoaua tlu'aquinone the whole is heated, while-stirring, for about? hours tothe boiling point After: cooling, the

of the nitrobenzene. V finished condensation .prbductis filtered,

washed; and dried. It is abrown powder,--

insoluble in water and alcohol, sparingly soluble in cold concentrated sulphuric acid to a reddish-brown solution. Its vat is redbrown and dyes cotton brown tints. 5 f

1 Example 10.

parts of diamihoanthraquinbn made by dinit'ratin'g anthra'quinone' and -.-reducing the nitration product, are introduced -together with 40 parts of cyanuric chloride into about 400 parts of mtrobenzcne, and

the whole is heated for anhour at PLO-145 I (3. After cooling, "the separated product is filtered. It is suspended in about @700 partsof nitrobenzene and afteradditiono'f 69 parts of monobenzoyl lA-diaminoanthr'aquinone the whole is heated for- 24: 'l10t11$ V at -160 C. while stirring. The mixture is then allowed to cool and the finished condensation product filtered, washed and dried. It is a .brown-red-powder insoluble in water, sparingly soluble in hoilingaalcohol and in hot nitrobenzene toa' bluish-red solution and soluble in cold concentrated brown-red vat dyes cotton copper tints.

Erample 11 l 223 .parts of l-aminoanthraguinone are introduced'together with parts ofcyasulphuric acid to a blue-red solution. 'Itsf loo nuric chloride into about 2,500'partsof nitrobenzene and the mixture is heated at 130 0., while stirring, for about hour. Aiter cooling the mixture is filtered. and the solid matter is washed and dried. 7 5- arts o'f this product and 24 parts of 1:8- iaminoanthraquinone are. introduced into 1,000

Ezrts of nitrobenzene and the 'mixture is iled in a-re'fiux apparatus for '6. hours. After cooling, the product is' filtered,

washed with alcohol and dried. It is a,

vlli) yellow powder soluble in-suphuric white at yellow solution and yielding a tints.

red-brown vat which dyes cotton fast reddish-yellow In all these eirain les there can be used,

as already mixture of both. he order in which the 'mits. named in the examples'others can1obvi'ousl be -used,-such as rimary-and secondary alkyL, aralkyl -lin arylamines, as-wellas other aminoanthraquinone derivatives, such.

stated, e her the pure-'kfiwor." 1:8-d ammoanthra fimone, or a" technical 12c operations are-performedand the. molecular roportions can be varied within -certain Instead of the amino=compounds as halogen amin'oanthraquinones and"hy-.--

droxy-aminoanthraquinones and their de-' r rivatives.

( s. meefar; t'ueimenmfaeee or.

series,' consisting in causing amino-compounds carrymg at least one reactlve hydlq'r; I

gen atom inthe aminocup; to react on II colnponnds'pf the genera formule;

i; I T v. 5"?) i, 1g}; wherein the letter 'ar presents the radical halogen??? 7:halogen I N L I "f and. r

we we the ween e:

n \rFerein-the:letteregrenresents the i j' 56 I II,

condensation y b l f the @nthi'uquimm?" seriesgconsistnig in reusing Yetv least' two mo lecuiaiy prgiiortion s'f of urom'atk; mine do zngonngs carrylmg ,at, one reactive and one Jof t1 1555. the two' letters ,bI hydrogeflg.

'I' 'if lheifrocess 'forfthe *i ng ueeme of V condensetwn roductsof the'anthmquinone ser1es, -cons1 stmg causing at least two'- ehthraquinone" Series Zearrym 'compoundecerrymg; at least one reective l etonilend flle other the radical lette -a a hydrogen on one molecular proportion of a compound l of the genera formula:

' I b 0 a a I I b I I I 4 wherein the letter e represents the radical re two letters he hydrogen 'ntom and the other the 'radical molecular proportions of 'eompoungie of the I I I I I 'riniary' ammo-groups; to meet on one mo ecu erpro? portion a cona'pon nd' of the general fo.

mule} I I .y' I I wherein the letter 'a. represents the radical I ff-KIWI! and bn the -twoiletter s bean-hydrogen Q t hal z xr- '5 (I -halogen I 1 H I I A general formule;

1 wherein the letter a represents a radical I (in which yanki' it"slre at leastione is an amino-radical which may m be subsituted), and wherein one of the two be substituted),

NH l.

substituents of which the others radical u letters by represents. a hydrogen atom and (in whichy. and z are substituents of which at least one is an amino radical which may which i products brownish-yellow to dark green powders red-brown so which dissolve in cold concentrated sulphuric acid to yellow to bluish-rcd-brown solution, andjn hot nitrobenzene to yellow to violet, brown and dirtvgreen solutions,

yielding vwith hydrosulphite and caustic soda solution red-brown tobordcaux and red-violet vats-irom which "cotton is dyed very fast reddish-yellow to red, brown and olive tints. v6. The herein described products of the general lprmula:

i b O a (in which y and z are substituents of which at least one is an aryhunino radical),'and wherein one of the two letters b represents a hydrogen atom and thcnother a radical green powders which dissolve in cold concer reted sulplhuric acid to yellow to bluish utions, and in hot nitrobenzene to yellow to violet, brown and dirty green solutions, yielding with hydrosul- ,Jhite and caustic soda. solution red-brown to bordeauxand red-violet vats from. which cotton is dyed very fast reddish-yellow to red, brown and olive tints.

7. The herein described mana e t e general formula:

' b -O a .b' v herein the letter a represents-a radical Jim y-d 0-2 i I zlrn l l (in which y and z are substituents of which at least one is an-arylaminoradical which contains an anthraquinone nucleus), and wherein one of the .two letters b represents a hydrogen atom and the other a radical (in which and z are s'ubstitucntsof which at least one is an arylam no radical which products form brownish-yellow to dark green powders which dissolve in cold con-' ccntrated sulphuric acid to yellow to bluish red-brown solutions, and in hot nitrobenzene to yellow to violet, brown and dirty green solutions, yieldin'g'with hydro sulphite and artistic sodasolntion red-brownto bordeaux 1nd red-violet vats from "which cotton is dyed very fast reddish-yellow to red, brown and olive tints.- o

8. The herein descrihcdproducts of thd general formula:

wherein the letter a ienresents a radical Ff, N

I 4 y v (in which y and zero substituents oi which contains an anthraquinone nucleus),- whichi I h 1,523 308 at ie l stfenei i s 5m anxi b-anthr ziqui rioiie padical), ami wherein one of the two 'letters b represntse. hydg'Oge'n atom and the other ara'dical w l: y I l m which 3 end z 517a subsmuents of which at} least-tone i -is fin amino-anthmquinone radical), form. brown- V i-sh'yenqw w r w issolve in, cm

concentx 'ated sulphufie a cid in hot ni- 115 trobenzene' $0 1 yellow so1ution,:gielding with hydrosulphite and; reaustic :50, a sdlution red-brown vat's from which"eottoniieif E dyedfeddish-yellowto Orange e 'tness].whe1 eof we have? hr'euntidib 'SlgQOd. our names this 26th day qf May, 1924, in, the presence of (we suhscribmg wit-j? nesses.

STEINBU H. FRANZ ACKEBMANN 

